Carrier composition and process for dyeing and printing

ABSTRACT

Carrier composition comprising a mixture of methylnapthalene and diphenylene oxide and the use thereof in the dyeing and printing of synthetic fibers.

United States Patent [191 Weckler et al.

[ July 29, 1975 CARRIER COMPOSITION AND PROCESS FOR DYEING AND PRINTING [75} Inventors: Gerhard Weckler, Sulzbach,

Taunus; Rolf Mildenberg, Mulheim (Ruhr) both of Germany [73] Assignee: Cassella Farbwerke Mainkur AG,

Germany [22] Filed: July 19, 1973 [21] Appl. No.: 380,534

[30] Foreign Application Priority Data July 26, 1972 Germany 2236551 [52] US. Cl. 8/173; 8/4; 8/93 [51] Int. Cl D06p 5/04 Primary Examiner-Donald Levy Attorney, Agent, or Firm-Connolly and Hutz [57] ABSTRACT Carrier composition comprising a mixture of methylnapthalene and diphenylene oxide and the use thereof in the dyeing and printing of synthetic fibers.

8 Claims, No Drawings CARRIER COMPOSITION AND PROCESS FOR DYEING AND PRINTING lt is known that the dyeing and printing of synthetic fiber materials such as polyester, cellulose acetate, polyvinyl chloride, polyolefin and other fibers or even combinations of synthetic and natural fibers suffer difficulties, particularly when deep shades are to be obtained at dyeing temperatures below 100C. It is further known that these difficulties may be reduced to some extent by the use of so-called carriers in the dyeing process. Carriers are understood to be chemical compositions which are added to the dye bath in a finely dispersed or emulsified form or are precipitated in the dye bath in a finely dispersed form and which promote the penetration of the dyestuff into the fiber, whereby a considerable increase in the color depth of the dyeings or prints is achieved.

Numerous compounds are already known as such carriers, such as, for example, and p-phenylphenol, methylnaphthalene, diphenyl, halogenated aromatic substances, aromatic carboxylic acids and esters thereof, as well as phenol derivatives and alcohols, ketones and amines.

In practice, however, only a few compounds have achieved importance. Methylnaphthalene is one of these. The use of methylnaphthalene as the carrier offers a disadvantage because a residue thereof remains on the dyed fiber and impairs fastness to light of the dyed and printed materials. The methylnaphthalene residue retained by the fibers may be removed as a practical matter only by a special heat treatment, temperatures of at least 150C. and processing times of at least 3 minutes being required. The required additional heat treatment makes the dyeing or printing process more expensive because of the expenditure of energy and apparatus and work requirements and prevents an uninterrupted course of work. In some instances, the processing times in the heat treatment may actually be shortened by elevation of the temperature. However, this possibility cannot be utilized in general because the fiber properties of textured polyester materials are impaired. In many instances, as for example in the dyeing of box thread, the mechanical conditions for the heat treatment, required for the removal of methylnaphthalene residues, are not present.

For the stated reasons, the use of methylnaphthalene as a carrier for the dyeing of synthetic fibers has remained limited to but a few areas, even though the methylnaphthalene otherwise has advantageous properties as a carrier. These include outstanding colordeepening effect in the dyeing and printing of polyester fibers, good emulsifiability, even dyeing effect and reasonable price.

It has now been found that the impairment of the fastness to lightof dyeings and prints brought about by methylnaphthalene may be reduced considerably, without impairing the otherwise advantageous carrier properties of methylnaphthalene, if a mixture of methylnaphthalene and diphenylene oxide are used as the carrier in place of methylnaphthalene.

The present invention relates therefor to a carrier composition, which contains methylnaphthalene and diphenylene oxide as the carrier-active substances, as well as a process for dyeing and printing of synthetic fibers, wherein this carrier composition is employed during the dyeing procedure.

As is the case with methylnaphthalene, diphenylene oxide is equally a readily accessible commercial product.

ln the context of the present invention, the term methylnaphthalene is understood to mean a-methylnaphthalene, B-methylnaphthalene or a mixture thereof.

In the novel carrier composition, the weight ratio between methylnaphthalene and diphenylene oxide is normally in the range of 1.2:1 to 4:1 and preferably in the range of 1.5:1 to 3:1.

The novel carrier composition may be employed with success in all dyeing and printing methods which are known for the dyeing and printing of synthetic fibers such as polyesters, e.g., polyethylene glycol terephthalate, cellulose triacetate, polyvinyl chloride, polyacrylonitrile, polyolefins, such as isotactic polypropylene and other synthetic fibers or mixtures thereof with natural fibers.

In the context of the present invention, the term fiber encompasses staple fibers, for example, and also thread, thread skeins, woven and knitted textiles, foils, flocks and other materials consisting of said polymers which can be dyed and printed.

In general, all dyestuffs capable of dyeing the polymers in question may be employed. Dispersion, developing and vat dyestuffs are especially preferred.

The novel carrier composition may be added to the dye liquor in a dispersed or emulsified form or dissolved in an organic solvent.

For the preparation of solutions, high-boiling organic solvents with a boiling point above C. are suitable, e.g., tetrahydronaphthalene, dimethylformamide, xylene, aromatic and aliphatic hydrocarbon halides such as benzene halides, esters such as benzene acid alkyl esters and alkylpolyglycol ethers. High-boiling petroleum distillates or mineral oils, as well as mixtures of various solvents, may also be employed.

Of the high-boiling petroleum distillates, particularly suitableis a transparent, non-toxic and weakly boiling distillate with a content of aromatic substances of about 99 by volume and a high flash point, which has a density of 0.877 g/cm and a boiling range of l62-180C.

Of the alkylpolyglycol ethers, particularly applicable are ethyl, propyl, butyl and pentyl polyglycol ethers.

The mixture of methylnaphthalene and diphenylene oxide is normally dissolved in sufficient solvent or solvent mixture to provide a weight ratio of solvent or solvent mixture to methylnaphthalene and diphenylene oxide of 4:1 to 0.5:1 preferably 2:1 to 1:1.

Particularly stable aqueous emulsions of a mixture of methylnaphthalene and diphenylene oxide are obtained in the dye bath if an emulsifier is added to the solution of the mixture of methylnaphthalene and diphenylene oxide in organic solvent or solvent mixture. In this preparation, the novel carrier composition is easily emulsifiable in the dye bath even without special precautions and may be poured into the dye bath directly without the usually required preemulsification with water.

The products or mixtures known to be carrier-active auxiliary agents may be used as emulsifiers. For example, anion-active substances include alkyl sulfates, e.g., sodium lauryl sulfate and sodium cetyl sulfate, turkey red oils, sulfonated oils, alkyl sulfonates and alkylaryl sulfates such as alkylbenzene sulfate and alkylnaphthalene sulfates. Nonionic reaction products include alkylene oxides with alkylphenols, alcohols, aliphatic saturated or unsaturated carboxylic acids, fatty amines and hydroxyl group'containing esters of saturated or unsaturated carboxylicacids.

The preferred emulsifier compositions are those disclosed in German published Application Nos. 1,619,489 and 1,802,210. These emulsifier compositions consist of mixtures of three components hereinafter called Component 1, Component 11 and Component lll. Component I is an addition compound of alkylene oxides and, free hydroxyl groups containing esters of saturated orunsaturated aliphatic carboxylic acids or hydroxycarboxylic acids with polyvalent alcohols having2-6 hydroxyl groups. Component I may also be an addition compound of alkylene oxides and alkyl phenols. Component 11 includes alkali metal and/or alkaline earth metal saltsof alkylbenzene sulfonic acids. Component 11 includes aliphatic primary or secondary alcohols with 3-6 carbon atoms.

' Reaction'produ'cts of alkali metal salts of alkylben- ,:%,.and preferably 3 to 15 of the methylnaphthalenediphenylene oxide composition, based on the weight of 1 the material to be dyed, is present in the dye liquor.

For printing, the novel carrier composition is dispersed in the printing paste. The actual printing process is then carried out in a manner known per se.

Drying of the dyeings or prints may be carried out under normal drying conditions, e.g., 30 seconds at 150C., without loss of fastness to light of the dyeings and prints. This is also true with respect to textured polyester material.

EXAMPLE 1 a. Five g. of a woven material consisting of polyethylene terephthalate fibers are treated in an aqueous dye bath at boiling temperature for l k hours in a liquor ratio of 1:40, the bath, based on the weight of the goods, containing 2 of the dispersion dyestuff of the formula as well as 3 g/l of a carrier preparation, which is obtained by simple stirring at room temperature, the following substances: i

25 parts by weight diphenylene oxide 40 parts by weight methylnaphthalene oil. containing over of a composition consisting of equal parts of aand B-methylnaphthalene 25 parts by weight 1,2,4-trichlorobenzene 10 parts by weight of an emulsifier mixture consisting of 5 parts by weight of an addition product of 36 mol ethylene oxide and 1 mol Castor oil 2.9 parts by weight isobutanol and 2.1 parts by weight of the calcium salt of tetrapropylene sulfonic acid.

The blue dyeing obtained is then treated for reductive purification for 20 minutes at 85C. with a solution containing, in one liter water:

2 g sodium dithionite,

2 ccsodium hydroxide of 38 Be and 0.5 g of a non-ionic washing agent.

b. The dyeing is repeated in the same manner as in (a) but using 3 g/l pure methylnaphthalene oil as the carrier in place of the carrier preparation indicated in (a).

For a comparison of the stability to light of the dyeings obtained in accordance with (a) and (b), both samples are dried for 30 seconds at 150C. after reductive purification and subsequently illuminated under the same conditions in a xeno-test apparatus. The dyeing (a), prepared using the novel carrier composition of this invention, has a considerably better fastness to light than the dyeing (b) prepared with pure methylnaphthalene carrier. I

Practically the same results are obtained when, under the above-stated dyeing conditions, the dyeing occurs with 2 based on the weight of the goods, of the dyestuff of the formula:

Using the dyestuffs C.l. Disperse Red 60, Cl. Disperse Blue 73, Disperse Red 160, Disperse Violet 47, Disperse Blue 165, Disperse Orange -71 and the novel carrier compositions, clearly better stabilities to light are obtained in the dyeing of polyester materials than when using methylnaphthalene as the carrier under comparable conditions.

What is claimed is:

1. A carrier composition comprising a mixture of methylnaphthalene and diphenylene oxide in a weight ratio of 1.2:1 to 4:1.

2. The carrier composition of claim 1 wherein said weight ratio is from 1.5:] to 3:1.

3. The carrier composition of claim 1 wherein the methylnaphthalene and diphenylene oxide are dissolved in an organic solvent having a boiling point of above C.

4. The carrier composition of claim 3 wherein the weight ratio between solvent and the mixture of meth ylnaphthalene and diphenylene oxide is 4:1 to 0.5:].

5. The carrier composition of claim 4 wherein said weight ratio is 2:1 to 1:1.

6. The carrier composition of claim 3 containing 5 to' 20% by weight emulsifier, based on the weight of the solution.

3 8 9 7 207 5 6 7. The carrier composition of claim 3 containing 7 to mote the penetration of the dyestuff into the fibers, the 10% by weight emulsifier, based on the weight of the solution.

8. In the process for dyeing and printing synthetic fiposmon of claim bers, wherein a carrier composition is employed to pro- 5 improvement which comprises using the carrier com- 

1. A CARRIER COMPOSITION COMPRISING A MIXTURE OF METHYLNAPHTHALENE AND DIPHENYLENE OXIDE IN A WEIGHT RATIO OF 1.2.:1 TO 4:1.
 2. The carrier composition of claim 1 wherein said weight ratio is from 1.5:1 to 3:1.
 3. The carrier composition of claim 1 wherein the methylnaphthalene and diphenylene oxide are dissolved in an organic solvent having a boiling point of above 100*C.
 4. The carrier composition of claim 3 wherein the weight ratio between solvent and the mixture of methylnaphthalene and diphenylene oxide is 4:1 to 0.5:1.
 5. The carrier composition of claim 4 wherein said weight ratio is 2:1 to 1:1.
 6. The carrier composition of claim 3 containing 5 to 20% by weight emulsifier, based on the weight of the solution.
 7. The carrier composition of claim 3 containing 7 to 10% by weight emulsifier, based on the weight of the solution.
 8. In the process for dyeing and printing synthetic fibers, wherein a carrier composition is employed to promote the penetration of the dyestuff into the fibers, the improvement which comprises using the carrier composition of claim
 1. 